Nanopatterned biosensor electrode for enhanced sensor signal and sensitivity

ABSTRACT

Methods for forming an electrode structure, which can be used as a biosensor, are provided in which the electrode structure has non-random topography located on one surface of an electrode base. In some embodiments, an electrode structure is obtained that contains no interface between the non-random topography of the electrode structure and the electrode base of the electrode structure. In other embodiments, electrode structures are obtained that have an interface between the non-random topography of the electrode structure and the electrode base of the electrode structure.

BACKGROUND

The present application relates to methods of forming an electrodestructure. More particularly, the present application relates to methodsof forming a nanopatterned electrode structure that can be used forbiosensing applications.

Biosensors with enhanced signal and sensitivity are essential to providereliable data for both medical and environmental monitoring. Suchbiosensors are especially needed for areas related to food and watersupply security as well as the healthcare industry. For healthcare,glucose sensors comprise a significant portion of the existing biosensormarket. Platinum (Pt) is commonly used as a working electrode in glucosesensors, and platinum has demonstrated biocompatibility. Externalelectrochemical sensors (so-called “Test-Strips”) are commonly used.However, limitations exist on the accuracy and applicability of teststrip sensors.

In vivo glucose sensors, which are implanted into a human body, can beused to continuously monitor blood sugar. However, the foreign bodyresponse restricts in vivo biosensors. Moreover, the foreign bodyresponse can reduce the sensor signal output over time.

Despite advances made in biosensor technology, there is still a need toprovide low-cost biosensors that exhibit enhanced sensor signal andsensitivity, and which may also mitigate the foreign body response.

SUMMARY

Methods for forming an electrode structure, which can be used as abiosensor, are provided in which the electrode structure has non-randomtopography located on one surface of an electrode base. In someembodiments, improved sensor signal and sensitivity can be obtained insuch an electrode structure if there is no interface between thenon-random topography of the electrode structure and the electrode baseof the electrode structure. By “no interface” is it meant that thenon-random topography and the electrode base are of unitary construction(i.e., one piece) and unitary composition (i.e., a same material). Otherembodiments include electrode structures that may have an interfacebetween the non-random topography of the electrode structure and theelectrode base of the electrode structure.

In one embodiment of the present application, a method of forming anelectrode structure is provided that includes providing a mold having apattern that comprises both an electrode base shape and a nanotopographyshape. A metallic seed layer and a conductive metal-containing materialare then formed to provide an electrode structure comprising theconductive metal-containing material and having the electrode base shapeand the nanotopography shape resulting from the influence of the mold.The mold is then removed from the electrode structure, and a biologicalfunctionalization material is then added to the electrode structure.

In another embodiment of the present application, a method of forming anelectrode structure is provided that includes providing an electrodebase having an electrode base shape on a substrate. Next, a patternedmaterial layer is formed surrounding the electrode base, wherein thepatterned material layer contains openings for defining a nanotopographyshape of the electrode structure. A metallic seed layer is then formedon exposed surfaces of the electrode base and within the openings of thepatterned material layer, and thereafter a conductive metal-containingmaterial is electroplated on the metallic seed layer and within theopenings of the patterned material layer to provide the electrodestructure comprising the electrode base having the electrode base shapeand the conductive metal-containing material having the nanotopographyshape. Next, the patterned material layer is removed, and thereafter, abiological functionalization material is attached to the electrodestructure.

In yet another embodiment of the present application, a method offorming an electrode structure is provided that includes providing anelectrode base material on a substrate. Next, a patterned material layeris formed surrounding the electrode base material, wherein the patternedmaterial layer contains openings. The electrode base material exposedsurface is then etched utilizing the patterned material layer as anetch-resistant mask to provide the electrode structure comprising aremaining portion of the electrode base material and having an electrodebase shape and a nanotopography shape, with no interface present betweenthe remaining portion of the electrode base material and thenanotopography. The patterned material layer is then removed, andthereafter a biological functionalization material is attached to theelectrode structure.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is a cross sectional view of an exemplary structure including afirst mask layer patterned to have an opening for defining an electrodebase shape and located on a surface of a substrate in accordance with anembodiment of the present application.

FIG. 2 is a cross sectional view of the exemplary structure of FIG. 1after transferring the electrode base shape into the substrate toprovide a patterned substrate having the electrode base shape andremoving the first mask layer from the resultant structure.

FIG. 3 is a cross sectional view of the exemplary structure of FIG. 2after forming a second mask layer patterned to have a plurality ofopenings that collectively define a nanotopography shape on thepatterned substrate.

FIG. 4 is a cross sectional view of the exemplary structure of FIG. 3after transferring the nanotopography shape into the patterned substrateto provide a mold containing the electrode base shape and thenanotopography shape and removing the second mask layer.

FIG. 5 is a cross sectional view of the exemplary structure of FIG. 4after forming a metallic seed layer on the exposed surfaces of the mold.

FIG. 6 is a cross sectional view of the exemplary structure of FIG. 5after electroplating a conductive metal-containing material to providean electrode structure comprising the conductive metal-containingmaterial and having the electrode base shape and the nanotopographyshape of the mold.

FIG. 7 is a cross sectional view of the exemplary structure of FIG. 6after removing excess conductive metal-containing material that may belocated above the electrode base shape of the mold.

FIG. 8 is a cross sectional view of the exemplary structure of FIG. 7after removing the mold from the electrode structure.

FIG. 9 is a three-dimensional representation of the electrode structurein accordance with an embodiment of the present application.

FIG. 10 is a cross sectional view of the exemplary structure of FIG. 8after the attachment of a biological molecule to the surface of theelectrode structure, which is also referred to as a functionalizationprocess.

FIG. 11 is a cross sectional view of an exemplary structure including asubstrate and an electrode base that can be used in accordance withanother embodiment of the present application.

FIG. 12 is a cross sectional view of the exemplary structure of FIG. 11after depositing a dielectric layer.

FIG. 13 is a cross sectional view of the exemplary structure of FIG. 12after forming a nanopattern array in the dielectric layer.

FIG. 14 is a cross sectional view of the exemplary structure of FIG. 13after forming a metallic seed layer on the exposed surfaces of theelectrode base.

FIG. 15 is a cross sectional view of the exemplary structure of FIG. 14after electroplating a conductive metal-containing material on themetallic seed layer.

FIG. 16 is a cross sectional view of the exemplary structure of FIG. 15after removing excess conductive metal-containing material that may belocated above the patterned dielectric layer.

FIG. 17 is a cross sectional view of the exemplary structure of FIG. 16after removing the patterned dielectric layer.

FIG. 18 is a cross sectional view of the exemplary structure of FIG. 11after depositing a photoresist layer.

FIG. 19 is a cross sectional view of the exemplary structure of FIG. 18after forming a nanopattern array in the photoresist layer.

FIG. 20 is a cross sectional view of the exemplary structure of FIG. 19after forming a metallic seed layer on exposed surfaces of the electrodebase.

FIG. 21 is a cross sectional view of the exemplary structure of FIG. 20after electroplating a conductive metal-containing material.

FIG. 22 is a cross sectional view of the exemplary structure of FIG. 21after performing a photoresist lift-off process.

FIG. 23 is a cross sectional view of the exemplary structure of FIG. 19after etching the exposed portions of the electrode base utilizing thepatterned photoreist layer as an etch mask.

FIG. 24 is a cross sectional view of the exemplary structure of FIG. 23after removing the patterned photoresist layer.

DETAILED DESCRIPTION

The present application will now be described in greater detail byreferring to the following discussion and drawings that accompany thepresent application. It is noted that the drawings of the presentapplication are provided for illustrative purposes only and, as such,the drawings are not drawn to scale. It is also noted that like andcorresponding elements are referred to by like reference numerals.

In the following description, numerous specific details are set forth,such as particular structures, components, materials, dimensions,processing steps and techniques, in order to provide an understanding ofthe various embodiments of the present application. However, it will beappreciated by one of ordinary skill in the art that the variousembodiments of the present application may be practiced without thesespecific details. In other instances, well-known structures orprocessing steps have not been described in detail in order to avoidobscuring the present application.

As mentioned above, methods for forming an electrode structure, whichcan be used as a biosensor, are provided in which the electrodestructure has non-random topography located on one surface of anelectrode base. In some embodiments, improved sensor signal andsensitivity can be obtained in such an electrode structure if there isno interface between the non-random topography of the electrodestructure and the electrode base of the electrode structure. By “nointerface” is it meant that the non-random topography and the electrodebase are of unitary construction (i.e., one piece) and unitarycomposition (i.e., a same material). Other embodiments include electrodestructures that may have an interface between the non-random topographyof the electrode structure and the electrode base of the electrodestructure.

Referring first to FIGS. 1-10, there is illustrated an embodiment of thepresent application in which a method is disclosed for forming anelectrode structure in which no interface is formed between thenon-random topography of the electrode structure and the electrode baseof the electrode structure.

Referring first to FIG. 1, there is illustrated an exemplary structureincluding a first mask layer 12P patterned to have an opening 14 fordefining an electrode base shape and located on a surface of a substrate10 in accordance with an embodiment of the present application. That is,the opening 14 has a shape that is used in the present application fordefining the electrode base of a resultant electrode structure to besubsequently formed. The shape of opening 14 may also include anycorresponding wiring for the electrode structure. In one embodiment,first mask layer 12P may be comprised of a photosensitive material suchas a photoresist. In an alternate embodiment, first mask layer 12P maybe comprised of dielectric film, hereafter referred to as a hardmask,which has been patterned using photolithography or other means known tothose skilled in the art.

The substrate 10 that can be employed in the present applicationincludes any material that can be readily patterned as described hereinand that can be subsequently removed from the resultant electrodestructure that is formed within a mold made from substrate 10.

In one embodiment of the present application, the substrate 10 iscomposed of a semiconductor material. The term “semiconductor material”denotes a material that has an electrical conductivity value between aconductor, such as copper, and an insulator, such as glass.Semiconductor materials may exist as elemental materials or compoundmaterials. Examples of semiconductor materials that may be used assubstrate 10 include Si, SiGe, SiGeC, SiC, Ge alloys, III/V compoundsemiconductors or II/VI compound semiconductors. In some embodiments ofthe present application, the substrate 10 may comprise a singlesemiconductor material. In other embodiments of the present application,the substrate 10 may comprise a multilayered stack of semiconductormaterials.

In one embodiment of the present application, the semiconductor materialthat can provide substrate 10 may be a single crystalline semiconductormaterial such as, for example, single crystalline silicon. By “singlecrystalline” it is meant a material in which the crystal lattice of theentire sample is continuous and unbroken to the edges of the sample,with no grain boundaries. In another embodiment of the presentapplication, the semiconductor material that can provide substrate 10may be a polycrystalline semiconductor material such as, for example,polycrystalline silicon. By “polycrystalline” it is meant a materialthat is composed of many crystallites (i.e., grains) of varying sizesand orientation. In yet a further embodiment of the present application,the semiconductor material that can provide substrate 10 may be anamorphous semiconductor material such as, for example, amorphoussilicon. By “amorphous” it is meant a material that lacks a long-rangecrystal order of a crystal.

In some embodiments of the present application, the semiconductormaterial that provides substrate 10 is a bulk semiconductor material. By“bulk” it is meant that the entirety of the substrate 10 is composed ofat least one semiconductor material. In one example, the substrate 10 isentirely composed of silicon.

Another material that may be used as substrate 10 is a dielectricmaterial. By “dielectric material” it is meant a material (i.e.,insulator) that does not conduct electricity readily. In one embodimentof the present application, the dielectric material that can providesubstrate 10 is composed of a semiconductor oxide such as, for example,silicon dioxide. In another embodiment of the present application, thedielectric material that can provide substrate 10 may be composed of asemiconductor nitride such as, for example, silicon nitride. Otherdielectric materials such as, for example, dielectric metal oxides,including aluminum oxide, may also be used as the material which can beused as the substrate 10.

In some embodiments, substrate 10 may be composed of a combination of asemiconductor material and a dielectric material. For example, substrate10 may be a material stack of, from bottom to top, a silicon dioxidelayer and a silicon layer. An optional handle substrate can be locatedbeneath the silicon dioxide layer. The optional handle substrate may becomposed of a semiconductor material, insulator, or conductive material.

Substrate 10 may also be composed of a ceramic material, an elementalmetal, an alloy of an elemental material or any other material orcombination of materials that can be readily patterned as describedherein and thereafter readily removed from an electrode structure thatis subsequently formed into a mold made from the material that providessubstrate 10.

The first mask layer 12P that can be used in the present application mayinclude a positive-tone photoresist material, a negative-tonephotoresist material, a hybrid photoresist material, or a hardmask layercomprised of a dielectric material. In one embodiment, the first masklayer 12P can be provided by first depositing a blanket layer ofphotoresist material on a surface of substrate 10. Following depositionof the blanket layer of photoresist material, the blanket layer ofphotoresist material is patterned to have an opening 14 that defines anelectrode base shape. When a hardmask layer is utilized, a blanket layerof a hardmask material (such as, silicon nitride) is first deposited andthereafter a patterned photoresist containing an opening that definesthe electrode base shape is formed atop the blanket layer of hardmaskmaterial. The pattern in the patterned photoresist is then transferredto the blanket hardmask material as an intermediate step, followed bysubsequent transfer of the pattern to the substrate 10. The transferringof the pattern may include one or more etching steps. The patternedphotoresist can be removed from atop the hardmask material anytime afterthe pattern has been transferred to the blanket layer of hardmaskmaterial.

The opening 14 defining the electrode base shape is not limited to anyspecific shape. In one embodiment of the present application, theopening 14 (and thus the electrode base shape) is a polygonal. In suchan embodiment, the opening 14 (and thus the electrode base shape) may betriangular, quadrilateral or pentagonal. In other embodiments, theopening 14 (and thus the electrode base shape) may be circular orelliptical. The opening 14 may also include additional structures suchas wiring or probe pads required to read out the electrical signal fromthe final electrode structure (not shown), thus resulting in a compoundshape for opening 14.

Referring now to FIG. 2, there is illustrated the exemplary structure ofFIG. 1 after transferring the electrode base shape into the substrate 10to provide a patterned substrate 10P having the electrode base shape 15and removing the first mask layer 12P from the resultant patternedsubstrate 10P. As is shown, the electrode base shape 15 does not extendthrough the entirety of the original substrate 10. Instead, some portionof the original substrate 10 remains beneath the electrode base shape 15after the pattern transfer process.

The transferring of the electrode base shape 15 defined by opening 14into the substrate 10 may be performed utilizing one or more etchingprocesses. Examples of etching processes that may be used in the presentapplication to transfer the electrode base shape 15 into the substrate10 may include dry etching, wet etching or any combination thereof. Dryetching may include one of reactive ion etching (RIE), ion beam etching,plasma etching, or laser ablation. Wet etching may include a chemicaletchant that is selective in removing the material that provides thesubstrate 10 relative to the mask layer material. The first mask layer12P can be removed from the patterned substrate 10P utilizing anyconventional resist stripping process such as, for example, oxygenashing or other chemical means. In some embodiments, a planarizationprocess may be used to remove the first mask layer 12P.

Referring now to FIG. 3, there is illustrated the exemplary structure ofFIG. 2 after forming a second mask layer 16P patterned to have aplurality of openings 18 that collectively define a nanotopography shapeon the patterned substrate 10P. By “nanotopography shape” it is meant anarray of non-random (i.e., regular repeating) individual articulatedfeatures whose size is less than the size of the electrode base shape15. In a preferred embodiment, at least one dimension of thenanotopography shape is less 1 um in size.

The plurality of openings 18 may have various shapes and sizes. Forexample, the plurality of openings 18 may have a shape of a circle, anellipse, or an annular structure. In one embodiment of the presentapplication, the plurality of openings 18 that is provided may have acritical dimension, i.e., diameter or width, from 5 nm to 900 nm. Inanother embodiment of the present application, the plurality of openings18 that is provided may have a critical dimension from 20 nm to 300 nm.

In one embodiment of the present application, each opening of theplurality of openings 18 has a pitch ratio of from 2:1 to 100:1. By“pitch” it is meant the center-to-center distance of nearest-neighborfeatures. The “pitch ratio” is defined based upon the critical dimensionof the feature, where the spacing between the features is proportionalto the critical dimension of the features. In another embodiment of thepresent application, each opening of the plurality of openings 18 has apitch ratio of from 2:1 to 20:1.

In one embodiment of the present application, the second mask layer 16Pis a photoresist material that can be formed and patterned as definedabove. In another embodiment, the second mask layer 16P is a dielectriclayer which can be patterned as defined above. In yet another embodimentof the present application, the second mask layer 16P is a component ofa block copolymer such as, for example, a self-assembling blockcopolymer. Notably, some block copolymers can be processed to include anordered pattern containing repeating structural units. In oneembodiment, the block copolymer may contain any numbers of the polymericblock components A and B arranged in any manner. For example, the blockcopolymer can have either a linear or a branched structure. In oneembodiment, the block copolymer is a linear diblock copolymer having theformula of A-B. Specific examples of suitable block copolymers that canbe used for forming the structural units may include, but are notlimited to: polystyrene-block-polymethylmethacrylate (PS-b-PMMA),polystyrene-block-polyisoprene (PS-b-PI),polystyrene-block-polybutadiene (PS-b-PBD),polystyrene-block-polyvinylpyridine (PS-b-PVP),polystyrene-block-polyethyleneoxide (PS-b-PEO),polystyrene-block-polyethylene (PS-b-PE),polystyrene-b-polyorganosilicate (PS-b-POS),polystyrene-block-polyferrocenyldimethylsilane (PS-b-PFS),polyethyleneoxide-block-polyisoprene (PEO-b-PI),polyethyleneoxide-block-polybutadiene (PEO-b-PBD),polyethyleneoxide-block-polymethylmethacrylate (PEO-b-PMMA),polyethyleneoxide-block-polyethylethylene (PEO-b-PEE),polybutadiene-block-polyvinylpyridine (PBD-b-PVP), andpolyisoprene-block-polymethylmethacrylate (PI-b-PMMA).

In order to form the ordered pattern containing repeating structuralunits, the block copolymer is first dissolved in a suitable solventsystem to form a block copolymer solution, which is then applied onto asurface to form a block copolymer layer, followed by annealing of theblock copolymer layer, thereby effectuating phase separation betweendifferent polymeric block components, i.e., first and second unitscontained in the block copolymer. The segregated block copolymer canthen be exposed, and developed to provide the second mask layer 16Phaving the plurality of openings 18.

Referring now to FIG. 4, there is illustrated the exemplary structure ofFIG. 3 after transferring the nanotopography shape provided by theplurality of openings 18 into the patterned substrate 10P to provide amold 10S containing the electrode base shape 15 and the nanotopographyshape 19 and removing the second mask layer 16P. As stated above, thenanotopography shape that is transferred into the patterned substrate10P includes an array of non-random (i.e., regular repeating) individualarticulated features (each non-random individual articulated feature islabeled as element 19 in FIG. 4) whose critical dimension is less thanthe size of the electrode base shape 15 provided on substrate 10.

As is shown in FIG. 4, the nanotopography shape including eachnon-random individual articulated feature 19 is formed within the areaincluding the electrode base shape 15. As is also shown, thenanotopography shape including each non-random individual articulatedfeature 19 may not extend through the entirety of the mold 10S. Instead,some portion of the mold 10S may remain beneath each non-randomindividual articulated feature 19 that collectively define thenanotopography shape after the pattern transfer process. In anotherembodiment (not shown), the nanotopography shape may extend entirelythrough the thickness of mold 10S.

Each non-random individual articulated feature 19 that is formedutilizing the second mask layer 16P has a shape, width, and pitchdefined by the plurality of openings 18 and the etching process used totransfer the pattern of openings 18 to the patterned substrate 10P. Forexample, each non-random individual articulated feature 19 may have ashape of a rod, a cone, an ellipse, or an annular structure. In oneembodiment of the present application, each non-random individualarticulated feature 19 may have a critical dimension ranging in sizefrom 5 nm to 900 nm. In another embodiment of the present application,each non-random individual articulated feature 19 may have a criticaldimension ranging in size from 20 nm to 300 nm.

In one embodiment of the present application, each non-random individualarticulated feature 19 has a pitch ratio of from 2:1 to 100:1.In anotherembodiment of the present application, each non-random individualarticulated feature 19 has a pitch ratio of from 2:1 to 20:1.

In one embodiment of the present application, each non-random individualarticulated feature 19 has a height from 5 nm to 300 μm. In anotherembodiment of the present application, each non-random individualarticulated feature 19 has a height from 50 nm to 20 μm.

In one embodiment of the present application, each non-random individualarticulated feature 19 has an aspect ratio (i.e., ratio of width toheight) of 1:1 to 500:1. In another embodiment of the presentapplication, each non-random individual articulated feature 19 has anaspect ratio (i.e., width to height) of 2:1 to 100:1.

The height and aspect ratio of each non-random individual articulatedfeature 19 is determined by the depth at which each non-randomindividual articulated feature 19 is formed into the patterned substrate10P.

The transferring of the nanotopography shape into the patternedsubstrate 10P can be achieved utilizing one of the etching processesmentioned above for transferring the electrode base shape into substrate10. In one embodiment of the present application, and when second masklayer 16P is composed of a photoresist material, the second mask layer16P can be removed utilizing a conventional resist developer such as,for example, ashing. In another of the present application, and when thesecond mask layer 16P is a component of a block copolymer or adielectric layer, second mask layer 16P can be removed utilizing anetchant that is selective in removing the component of the blockcopolymer or dielectric layer.

Referring now to FIG. 5, there is illustrated the exemplary structure ofFIG. 4 after forming a metallic seed layer 20 on the exposed surfaces ofthe mold 10S. The metallic seed layer 20 (which may also be referred toas a plating seed layer) includes any metal or metal alloy that canfacilitate the subsequent electroplating of a conductivemetal-containing material (to be subsequently described). The metallicseed layer 20 may include platinum, copper, silver, gold, tungsten,aluminum, iron, palladium, nickel, titanium, zirconium or any alloythereof. The metallic seed layer 20 typically includes the sameconductive metal or metal alloy as the subsequently formed conductivemetal-containing material 22. For example, a copper seed layer is usedfor electroplating a copper layer.

The metallic seed layer 20 may have a thickness from 5 nm to 25 nm,although other thicknesses that are lesser than 5 nm, and greater than25 nm can be used in the present application. In the illustratedembodiment of the present embodiment, the metallic seed layer 20 iscontinuous layer which can be formed utilizing a deposition process suchas, for example, chemical vapor deposition, plasma enhanced chemicalvapor deposition, atomic layer deposition or physical vapor deposition.

Referring now to FIG. 6, there is illustrated the exemplary structure ofFIG. 5 after electroplating a conductive metal-containing material 22 onthe metallic seed layer 20 to provide an electrode structure having theelectrode base shape and the nanotopography shape of the mold 10S. Theconductive metal-containing material 22 may consist of an elementalmetal or an alloy containing one or more elemental metals. Examples ofelemental metals that may be employed as the conductive metal-containingmaterial 22 include, but are not limited to platinum, copper, silver,gold, tungsten, aluminum, iron, palladium, nickel, titanium, orzirconium. Since in an ideal embodiment the metallic seed layer 20 iscomposed of the same material as the conductive metal-containingmaterial 22, the metallic seed layer 20 is not separately shown in thesubsequent drawings of the present application.

As mentioned above, the conductive metal-containing material 22 isformed utilizing an electroplating process. Electroplating is a processthat uses electrical current to reduce dissolved metal cations presentin an electroplating bath (i.e., an electrolyte) so that the metalcations form a coherent metal coating on an electrode.

When conductive metal-containing material 22 is introduced in theelectrode base shape 15, the resulting structure provides an electrodebase 22S of the electrode structure, while the nanotopography shape 19provides non-random topography in the form of repeating individuallyarticulated features 22P of the electrode structure. In accordance withthis embodiment of the present application, the electrode base 22S ofthe electrode structure, and the non-random topography provided by therepeating individually articulated features 22P are of unitaryconstruction (i.e., single piece) and of a same composition. Thus, theelectrode structure (22S, 22P) that is provided lacks an interfacebetween the electrode base 22S and the non-random topography provided bythe repeating individually articulated features 22P. Each repeatingindividually articulated feature 22P that is provided has a shape,width, pitch, height and aspect ratio as defined above for eachnon-random individual articulated feature 19.

Referring now to FIG. 7, there is illustrated the exemplary structure ofFIG. 6 after removing excess conductive metal-containing material 22that is located above the electrode base shape 15 of the mold 10S. Afterthe excess conductive metal-containing material 22 is removed, theresultant electrode structure (22S, 22P) has a planar surface that isopposite the surface that includes the non-random topography in the formof repeatable non-random individually articulated features 22P.

In one embodiment of the present application, the removal of the excessconductive metal-containing material 22 may be performed by aplanarization process such as, for example, chemical mechanicalplanarization and/or grinding. In another embodiment of the presentapplication, the removal of the excess conductive metal-containingmaterial 22 may be performed by utilizing at least one etch process suchas, for example, a chemical etch back process and/or a reactive ion etch(RIE) process.

Referring now to FIG. 8, there is illustrated the exemplary structure ofFIG. 7 after removing the mold 10S from the electrode structure (22S,22P). In some embodiments of the present application, the mold 10S canbe removed by completely dissolving the mold 10S utilizing a wetchemical etchant. In another embodiment, the mold 10S may be removedusing reactive ion etching (RIE). In such embodiments, the mold 10S is asingle-use mold.

In some embodiments, the mold 10S may be removed by releasing theresultant electrode structure (22S, 22P) from the mold 10S. In such anembodiment, the mold 10S may be reused multiple times. In such aninstance, a release agent such as, for example, silicone, may be appliedto the inside of the mold 10S prior to introducing the conductivemetal-containing material 22 into the mold 10S. The release agent mayinclude any chemical that can prevent bonding of the conductivemetal-containing material to the exposed surfaces of mold 10S.

Referring now to FIG. 9, there is illustrated a three-dimensionalrepresentation of the electrode structure (22S, 22P) in accordance withan embodiment of the present application. In this embodiment, eachnon-random individual articulated feature 22P that provides thenon-random topography of the electrode structure is in the shape of ananorod that extends upward from the electrode base 22S. Additionalcorresponding wiring and/or associated probe pads required forinterpretation of the electrical signal may also be included (notshown).

After forming the electrode structure shown in FIG. 8 or FIG. 9, inorder to functionalize the structure to respond as a biosensor, abiological functionalized material 24 can be applied to the surface ofthe electrode structure (22S, 22P) as shown in FIG. 10, including eachnon-random individual articulated feature 22P that provides thenanotopography shape of the electrode structure of the presentapplication. Any of the exposed areas of the electrode base 22S may alsobe coated with the biological functionalization material 24. Theelectrode structure (22S, 22P) can be used as a component in variousbiosensors which include other well-known components, such as but notlimited to, reference and counter electrode structures.

By “biological functionalization material” it is meant any bioreceptorthat binds with a complementary target biomolecule to create a bindingevent. In the primary embodiment, biochemical reactions involving thebiological functionalization material generate an electrical signalwhich can be conducted by the non-random individual articulated feature22P of the electrode structure of the present application under anapplied electric potential. Examples of biological functionalizationmaterials that can be used in the present application include anoligonucleotide, a nucleic acid, a peptide, a ligand, a protein, anenzyme, or any other material apt to bind with a complementary targetbiomolecule. When the electrode structure (22P, 22S) of the presentapplication is used for glucose sensing, the biologicalfunctionalization material 24 can be composed of glucose oxidase orglucose dehydrogenase.

The biological functionalization material 24 can be applied to theelectrode structure (22S, 22P) of the present application utilizingestablished biological functionalization processes known to thoseskilled in the art. Such biological functionalization processestypically include a series of chemical reactions that attach thebiological functionalization material 24 on the surface of the electrodestructure of the present application.

Referring now to FIGS. 11-17, there is illustrated an embodiment of thepresent application in which a method is disclosed for forming anelectrode structure in which an interface is formed between thenon-random topography of the electrode structure and the electrode baseof the electrode structure.

Referring first to FIG. 11, there is illustrated an exemplary structureincluding a substrate 50 and an electrode base 52 that can be used inaccordance with another embodiment of the present application. In someembodiments, other portions of the substrate 50 not containing theelectrode base 52 can be protected with a protective dielectric material(not shown).

The substrate 50 that can be used in this embodiment of the presentapplication may include one of materials mentioned above for substrate10. In one example, substrate 50 may be a semiconductor substrate suchas, for example, silicon.

An electrode base 52 can then be formed atop a portion of the substrate50. The electrode base 52 may be formed by deposition of a conductivematerial and then patterning the conductive material utilizing any wellknown patterning process such as, for example, photolithography andreactive ion etching. In one embodiment of the present application, theconductive material may include one of the conductive metal-containingmaterials mentioned above for conductive metal-containing material 22.In this embodiment, the electrode base 52 has an electrode base shape asdefined above.

Referring now to FIG. 12, there is illustrated the exemplary structureof FIG. 11 after depositing a dielectric layer 54. Dielectric layer 54may include any hardmask material such as, for example, silicon nitride.The dielectric layer 54 may be formed utilizing any deposition processsuch as, for example, chemical vapor deposition or plasma enhancedchemical vapor deposition. The dielectric layer 54 may have a height andwidth that is greater than the height or width of the electrode base 52.

Referring now to FIG. 13, there is illustrated the exemplary structureof FIG. 12 after forming nanotopography on the dielectric layer 54. Thenanotopography can be formed utilizing any patterning process including,for example, photolithography and reactive ion etching. The patterningprocess provides a patterned dielectric layer 54P that has openings thatexpose portions of the surfaces of the underlying electrode base 52. Theopenings have the shape and size of a non-random individual articulatedfeature, as defined above, and thus collectively define thenanotopography shape of the electrode structure of the presentapplication.

Referring now to FIG. 14, there is illustrated the exemplary structureof FIG. 13 after forming a metallic seed layer 20 on exposed surface ofthe electrode base 52. The metallic seed layer 20 of this embodiment ofthe present application is the same as the metallic seed layer mentionedin the previous embodiment of the present application. In thisembodiment of the present application, the metallic seed layer 20 can beformed by a selective deposition process such that the metallic seedlayer 20 is formed only upon the exposed surfaces of the electrode base52. In an alternate embodiment, metallic seed layer 20 may be renderedunnecessary if electrode base 52 is of a design and material to allowsubsequent processing without the presence of a metallic seed layer.Alternatively, a contiguous layer of metallic seed material can beformed as described in the previous embodiment of the presentapplication.

Referring now to FIG. 15, there is illustrated the exemplary structureof FIG. 14 after electroplating a conductive metal-containing material22 on the metallic seed layer 20. The conductive metal-containingmaterial 22 that is employed in this embodiment of the presentapplication is the same as that described above for the previousembodiment of the present application. The conductive metal-containingmaterial 22 of this embodiment can be formed as described above in theprevious embodiment of the present application. Since the metallic seedlayer 20 may be composed of the same material as the conductivemetal-containing material 22, the metallic seed layer 20 is notseparately shown in the drawings of the present application. In thisembodiment of the present application, electrode base 52 has theelectrode base shape, while the conductive metal-containing material 22that is formed within the openings present in the patterned dielectriclayer 54P collectively define the nanotopography shape of the electrodestructure of the present application.

In some embodiments, the conductive metal-containing material 22 maycontain a same conductive material as the electrode base 52. In anotherembodiment, the conductive metal-containing material 22 contains adifferent conductive material than the conductive material that providesthe electrode base 52.

Referring now to FIG. 16, there is illustrated the exemplary structureof FIG. 15 after removing excess conductive metal-containing material 22that may be located above the patterned dielectric layer 54P. After theexcess conductive metal-containing material 22 is removed, an electrodestructure (52, 22P) is formed that includes the electrode base 52 andnon-random individual articulated features 22P that provides thenanotopography shape of the electrode structure of this embodiment ofthe present application.

In one embodiment of the present application, the removal of the excessconductive metal-containing material 22 may be performed by aplanarization process such as, for example, chemical mechanicalplanarization and/or grinding. In another embodiment of the presentapplication, the removal of the excess conductive metal-containingmaterial 22 may be performed by utilizing at least one etch process suchas, for example, a chemical etch back process and/or a reactive ion etch(RIE) process. In either embodiment, the removal process provides astructure in which the topmost surface of each of the non-randomindividual articulated features 22P is coplanar with the topmost surfaceof the patterned dielectric layer 54P.

Referring now to FIG. 17, there is illustrated the exemplary structureof FIG. 16 after removing the patterned dielectric layer 54P. Thepatterned dielectric layer 54P may be removed utilizing any removalprocess that is selective in removing the dielectric material thatprovides the patterned dielectric layer 54P relative to a conductivemetal or the material of the substrate 50. In some embodiments, areactive ion etch may be employed to remove the patterned dielectriclayer 54P. In another embodiment, a chemical wet etch process may beused to remove the patterned dielectric layer 54P. In yet anotherembodiment, patterned dielectric layer 54P may be recessed such that thetop surfaces of electrode structure 52 are exposed while the sidewallsof electrode structure 52 remain covered by patterned dielectric layer54P.

In some embodiments of the present application, the substrate 50 can beremoved from beneath the electrode structure (52, 22P) shown in FIG. 17to provide a free-standing electrode structure (52, 22P). The removal ofthe substrate 50 may be performed utilizing a planarization process orseries of processes such, as for example, chemical mechanicalplanarization or mechanical grinding. The electrode structure (52, 22P)can be functionalized to respond as a biosensor. Notably, a biologicalfunctionalization material as defined above can be applied to thesurface of the electrode structure (52, 22P) provided in FIGS. 11-17.

Referring now to FIGS. 18-22, there is illustrated an embodiment of thepresent application in which a method is disclosed for forming anelectrode structure in which an interface is formed between thenon-random topography of the electrode structure and the electrode baseof the electrode structure. This embodiment of the present applicationbegins by first providing the exemplary structure shown in FIG. 11.

Referring first to FIG. 18, there is illustrated the exemplary structureof FIG. 11 after depositing a photoresist layer 60. Photoresist layer 60may include a positive-tone or negative-tone photoresist material. Thephotoresist layer 60 may be formed utilizing any deposition process suchas, for example, spin-on coating. The photoresist layer 60 may have aheight and width that is greater than the height or width of theelectrode base 52.

Referring now to FIG. 19, there is illustrated the exemplary structureof FIG. 18 after patterning the photoresist layer 60. The patterning canbe performed by exposing and developing the photoresist layer utilizingphotolithography. The nanopatterning provides a patterned photoresistlayer 60P including openings that expose surfaces of the underlyingelectrode base 52. The openings have the shape and size of a non-randomindividual articulated feature, as defined above, and thus collectivelydefine the nanotopography shape of the electrode structure of thepresent application.

Referring now to FIG. 20, there is illustrated the exemplary structureof FIG. 19 after forming a metallic seed layer 20 on exposed surface ofthe electrode base 52. The metallic seed layer 20 of this embodiment ofthe present application is the same as the metallic seed layer mentionedin the previous embodiment of the present application. In thisembodiment of the present application, the metallic seed layer 20 can beformed by a selective deposition process such that the metallic seedlayer 20 is formed only upon the exposed surfaces of the electrode base52. Alternatively, a contiguous layer of metallic seed material can beformed as described in the previous embodiment of the presentapplication.

Referring now to FIG. 21, there is illustrated the exemplary structureof FIG. 20 after electroplating a conductive metal-containing material22 on the metallic seed layer 20. The conductive metal-containingmaterial 22 that is employed in this embodiment of the presentapplication is the same as that described above for the previousembodiment of the present application. The conductive metal-containingmaterial 22 of this embodiment can be formed as described above in theprevious embodiment of the present application. Since the metallic seedlayer 20 may be composed of the same material as the conductivemetal-containing material 22, the metallic seed layer 20 is notseparately shown in the drawings of the present application. In thisembodiment of the present application, electrode base 52 has theelectrode base shape, while the conductive metal-containing material 22that is formed within the openings present in the patterned photoresistlayer 60P collectively define the nanotopography shape of the electrodestructure of the present application.

In some embodiments, the conductive metal-containing material 22 maycontain a same conductive material as the electrode base 52. In anotherembodiment, the conductive metal-containing material 22 contains adifferent conductive material than the conductive material that providesthe electrode base 52.

Referring now to FIG. 22, there is illustrated the exemplary structureof FIG. 21 after performing a lift-off process to remove the excesspatterned photoresist layer 60P. After performing the lift-off process,an electrode structure (52, 22P) is formed that includes the electrodebase 52 and non-random individual articulated features 22P that providesthe nanotopography shape of the electrode structure of this embodimentof the present application.

The lift-off process that can be used in the present applicationincludes any conventional lift process that can remove the material thatprovides the patterned photoresist layer 60P. During the lift-offprocess portions of the conductive metal-containing material 22 locateddirectly atop the patterned photoresist layer 54P can be removed. Afterperforming the lift-off process, a planarization process may be used toprovide the non-random individual articulated features 22P of theelectrode structure of this embodiment of the present application.

In some embodiments of the present application, the substrate 50 can beremoved from beneath the electrode structure (52, 22P) shown in FIG. 22to provide a free-standing electrode structure (52, 22P). The removal ofthe substrate 50 may be performed utilizing a planarization process orseries of processes such as, for example, chemical mechanicalplanarization and mechanical grinding. The electrode structure (52, 22P)can be functionalized with a biologically active layer to respond as abiosensor. Notably, a biological functionalization material as definedabove can be applied to the surface of the electrode structure (52, 22P)provided in FIGS. 18-22.

Referring now to FIGS. 23-24, there is illustrated an embodiment of thepresent application in which a method is disclosed for forming anelectrode structure in which no interface is formed between thenon-random topography of the electrode structure and the electrode baseof the electrode structure. This embodiment of the present applicationbegins by providing either the exemplary structure shown in FIG. 13 orFIG. 19. For illustrative purposes, the exemplary structure shown inFIG. 19 is shown. When the exemplary structure shown in FIG. 13 is used,the etching of the exposed portions of the electrode base 52 asdisclosed herein below can be used utilizing the patterned dielectriclayer 54P as an etch mask. After etching the patterned dielectric layer54P can be removed as disclosed in the second embodiment mentionedabove. In this embodiment of the present application and unlike theprevious embodiments, the initial electrode base 52 does not yet havethe electrode base shape; in this embodiment the electrode base thatdoes not have the electrode base shape may be referred to merely as anelectrode base material. Instead, the electrode base shape is defined bythe openings that are present in the patterned photoresist layer 60 andthe depth of the etch, while the portions of the patterned photoresistlayer 60P atop the electrode base material and the depth of the etchcollectively define the nanotopography shape of the electrode structureof the present application.

Referring now to FIG. 23, there is illustrated the exemplary structureof FIG. 19 after etching the exposed portions of the electrode basematerial utilizing the patterned photoreist layer 60P as an etch mask.The etching of the exposed portions of the electrode base materialprovides an electrode structure of the present application. Theelectrode structure includes electrode base 52S having non-randomtopography provided by individual articulated features 52P located onone surface of the electrode base 52S. In accordance with thisembodiment of the present application, the electrode base 52S and thenon-random topography provided by the individual articulated features52P are of uniform construction and uniform composition.

The etching of the exposed portions of the electrode base material canbe performed utilizing an anisotropic etch process. In one example, theanisotropic etch process is a dry etching process such as, for example,reactive ion etching. In another example, the anisotropic etch processis a chemical wet etch process in which a chemical etchant thatselectively removes the material that provides the electrode basematerial relative to photoresist material.

Referring now to FIG. 24, there is illustrated the exemplary structureof FIG. 23 after removing the patterned photoresist layer 60P. Theremoval of the patterned photoresist may be performed utilizing anyphotoresist stripping process such, as for example, oxygen plasma-basedashing. As is shown in FIG. 24, the removal of the patterned photoresistlayer 60P from the exemplary structure shown in FIG. 23 provides anelectrode structure that includes electrode base 52S having non-randomtopography provided by individual articulated features 52P located onone surface of the electrode base 52S; the electrode base 52S which nowhas electrode base shape is composed of remaining portions of electrodebase material. In accordance with this embodiment of the presentapplication, the electrode base 52S and the non-random topographyprovided by the individual articulated features 52P are of uniformconstruction and uniform composition.

In some embodiments of the present application, the substrate 50 can beremoved from beneath the electrode structure (52S, 52P) shown in FIG. 24to provide a free-standing electrode structure (52S, 52P). The removalof the substrate 50 may be performed utilizing a planarization processor series of processes such as, for example, chemical mechanicalplanarization and mechanical grinding. The electrode structure (52S, 52Pcan be functionalized to respond as a biosensor. Notably, a biologicalfunctionalized material as defined above can be applied to the surfaceof the electrode structure (52S, 52P) provided in FIGS. 23-24.

While the present application has been particularly shown and describedwith respect to preferred embodiments thereof, it will be understood bythose skilled in the art that the foregoing and other changes in formsand details may be made without departing from the spirit and scope ofthe present application. It is therefore intended that the presentapplication not be limited to the exact forms and details described andillustrated, but fall within the scope of the appended claims.

What is claimed is:
 1. A method of forming an electrode structure, themethod comprising: providing an electrode base having an electrode baseshape on a substrate; forming a patterned material layer on andsurrounding the electrode base, wherein the patterned material layercontains openings that physically expose the electrode base and define ananotopography shape of the electrode structure; forming a metallic seedlayer on the physically exposed surfaces of the electrode base andwithin the openings; electroplating a conductive metal-containingmaterial on the metallic seed layer and within the openings to providethe electrode structure comprising the electrode base having theelectrode base shape and the conductive metal-containing material havingthe nanotopography shape; removing the patterned material layer; andattaching a biological functionalization material to the electrodestructure.
 2. The method of claim 1, wherein the patterned materiallayer is composed of a dielectric material, and the substrate iscomposed of a semiconductor material.
 3. The method of claim 1, whereinthe patterned material layer is composed of a photoresist material, andthe substrate is composed of a semiconductor material.
 4. The method ofclaim 1, further comprising: removing the substrate, wherein theremoving of the substrate is performed between the removing of thepatterned material layer and the attaching of the biologicalfunctionalization material to the electrode structure.
 5. The method ofclaim 1, wherein the metallic seed layer and the conductivemetal-containing material comprise a same metal or metal alloy.
 6. Themethod of claim 1, wherein the biological functionalization material iscomposed of an oligonucleotide, a nucleic acid, a peptide, a ligand, aprotein, an enzyme, or any other material apt to bind with acomplementary target biomolecule.
 7. The method of claim 6, wherein thebiological functionalization material is composed of glucose oxidase orglucose dehydrogenase.
 8. The method of claim 1, wherein an interface ispresent between the electrode base shape and the nanotopography shape.9. The method of claim 1, wherein the providing of the electrode basehaving the electrode base shape comprises: depositing a conductivematerial on the substrate; and patterning the conductive material. 10.The method of claim 9, wherein the conductive material is a conductivemetal-containing material selected from an elemental metal and an alloycontaining one of more elemental metals.
 11. The method of claim 10,wherein the elemental metal is platinum, copper, silver, gold, tungsten,aluminum, iron, palladium, nickel, titanium or zirconium.
 12. The methodof claim 1, wherein the forming of the metallic seed layer comprises aselective deposition process.
 13. The method of claim 1, wherein theconductive metal-containing material has a topmost surface that iscoplanar with a topmost surface of the patterned material layer.
 14. Themethod of claim 13, wherein the electroplating of the conductivemetal-containing material further comprises removing excess conductivemetal-containing material that extends outside of the openings.
 15. Themethod of claim 14, wherein the removing of the excess conductivemetal-containing material comprises a planarization process or an etchback process.
 16. The method of claim 1, wherein the removing of thepatterned material layer comprises recessing the patterned materiallayer to physically expose a topmost surface of the electrode structure,while maintaining said patterned material layer along the sidewalls ofthe electrode structure.
 17. The method of claim 1, wherein the removingof the patterned material layer comprises a reactive ion etch or achemical wet etch.
 18. A method of forming an electrode structure, themethod comprising: providing an electrode base having an electrode baseshape on a substrate; forming a patterned material layer on andsurrounding the electrode base, wherein the patterned material layercontains openings that physically expose the electrode base and define ananotopography shape of the electrode structure; electroplating aconductive metal-containing material within the openings to provide theelectrode structure comprising the electrode base having the electrodebase shape and the conductive metal-containing material having thenanotopography shape; removing the patterned material layer; andattaching a biological functionalization material to the electrodestructure.
 19. The method of claim 18, further comprising: removing thesubstrate, wherein the removing of the substrate is performed betweenthe removing of the patterned material layer and the attaching of thebiological functionalization material to the electrode structure. 20.The method of claim 18, wherein an interface is present between theelectrode base shape and the nanotopography shape.